Chrome containing azomethine dyestuffs



United States Patent 2,7 53,344 CHROME CONTAINING AZOMETHINE DYESTUFFS Karl Schmidt, Leverkusen-Bayerwerk, Werner Miiller,

Koln, Rolf Piitter, Dusseldorf, Fritz Suckfiill and Gerhard Dittmar, Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany N0 Drawing. Application March 30, 1954, Serial No. 419,908 Claims priority, application Germany April 4, 1953 8 Claims. (Cl. 260-240) The present invention relates to new chrome containing azomethine dyestulfs and to a process of making the same; more particularly it relates to the chrome complex compounds of o,o-dihydroxyazomethine dyestuffs free from sulfonic or carboxylic acid groups corresponding to the following general formula 1 wherein the radicals R are aromatic radicals of which at least one contains an alkylsulfone group and R stands for hydrogen or an organic radical. The alkylsulfone groups attached to one or both radicals R may be linked thereto either as open chain radical or as ring.

In French Patent 811,814 and its patents of addition 49,406 and 49,497 there is described a manufacture of metal containing o,o-dihydroxyazomethine dyestuffs which are distinguished by good fastness properties. The chrome containing dyestufis with a sulfonic acid group in the molecule dye wool from strongly sulfuric acid dyebath; the dyeings are likewise distinguished by good fastness properties. The shades of the chrome containing dyestuffs obtained according to the processes of the mentioned patents are limited substantially to yellow. If in dyeing these dyestuffs weakly acid dye-baths are employed no full and fast dyeings are obtained.

We have now found that new valuable chromium complex compounds of 0,0'-dihydroxyazomethine dyestuffs can be obtained, if in their preparation components are used which contain alkylsulfone groups either as open chain radicals or as ring. Typical representatives of these alkylsulfone groups are S02.CH3 (open chain) and -SO2.CH2.O (ring). The sulfone ether starting materials may be obtained as disclosed in copending application S. N. 366,616 of common assignment, filed July 7, 1953.

These new dyestuffs can be made by condensing o-hydroxycarbonyl compounds of the general formula wherein R is an aromatic radical, R stands for hydrogen or an organic radical, with aromatic o-hydroxyamino compounds in the presence of chromium yielding agents in water or organic solvents or solvent mixtures, one of the two components or both containing in the aromatic radical alkylsulfone groups either as open chain radical or as ring. The aromatic radicals may contain further substituents except sulfonic or carboxylic acid groups.

'ice

naphthaldehyde, the aldehyde of hydroquinone methylene sulfone ether of the formula H l5-hydroxybenzoxathiol-S-dioxide-4-aldehyde1, the naphthohydroquinone methylene sulfone ether aldehyde of the formula OCH2 [4' hydroxynaphtho (2',l':4,5 oxathiol S dioxide- 3-aldehyde].

Suitable aromatic o-hydroxyamino compounds are e. g. Z-amino-I-hydroxybenzene, Z-amino-l-hydroxybenzene- 4-sulfonamide, 4-nitro-6-chloro-2-amino-l-hydroxybenzene, 4,6-dinitro-2-amino-l-hydroxybenzene, 3,4,6-trichloro-2-amino-l-hydroxybenzene, Z-amino-l-hydroxybenzene-4-methylsulfone, aminohydroquinone methylene sulfone ether of the formula [4-amino-5-hydroxybenzoXathiol-S-dioxidel The new chrome containing dyestuffs are distinguished over the hithero known comparable dyestuffs particularly by the fact that they possess a water-solubility sufficient for the dyeing-process in spite of the absence of acid water-solubilizing groups and that they yield full and fast shades on animal fibres from neutral to weakly acid dye-baths. A further valuable and surprising property of the new dyestuffs are the shades they yield which show compared with the hitherto known chrome containing azomethine dyestuffs, an unexpected and strong deepening; according to the components used in the manufacture of the dyestuffs the shades are shifted to the blue side of the spectrum far beyond red.

The following examples illustrate the present invention without, however, limiting it thereto; the parts being by weight:

Example 1 7.83 parts of S-chloro-Z-hydroxybenzaldehyde and 10.05 parts of aminohydroquinone methylene sulfone other are heated in 150 parts of formamide for half an hour to a temperature of about C. At this temperature a solution of 4.26 parts of potassium bichrornate (lQCrzOv) and 7.83 parts of glucose in parts of water is dropped in within one hour, and the solution is heated for further 1 /2 hours to about 95 C. After cooling, the separated deposit is sucked otf, washed with 250 parts of cold water and dried. The new chromium complex of the dyestuif of the formula OH HCI) U dyes Wool from a neutral and Weakly acetic bath reddish orange shades. The dyeing is fast to washing and to light. The dyestuif shows a good levelling power.

Example 2 OH H are obtained. The dyestuff dyes wool from a neutral and weakly acetic bath clear reddish orange shades. The dyeing is fast to rubbing and to washing. The levelling power is good.

Example 3 By replacing the quantity of the -bromo-2-hydroxybenzaldehyde mentioned in Example 2 by 9.54 parts of 3,5 dichloro-Z-hydroxybenzaldehyde and further carrying out the process as described therein, 9.2 parts of a brown dyestufi powder being the chrome complex of are obtained. When dyed on wool from a neutral or weakly acetic bath, the chromium complex yields a strongly reddish orange dyeing (distinctly redder than that with the dyestuff of Example 2) showing good fastness to washing and to light.

Example 4 By replacing the quantity of the S-bromo-Z-hydroxybenzaldehyde mentioned in Example 2 by 10.04 parts of 3-nitro-5-chloro-2-hydroxybenzaldehyde and further carrying out the process as described therein, the chromium complex of the azomethine dyestufi of the formula OH HO OzN- CH=N 1 HaCO is obtained which dyes wool from a neutral or weakly acetic bath brownish red.

Example 5 8.6 parts of 2-hydroxy-l-naphthaldehyde and 10.05 parts of aminohydroquinone methylene sulfone ether are heated in 150 parts of formamide for half an hour to about 95 C. 63.2 parts of an aqueous solution of sodiumpotassium chrome-salicylate corresponding to 1.56 parts of chromium are then run in. The solution obtained is heated on the boiling water bath for 3 hours; after cooling the reaction mixture it is introduced into 500 cc. of cold water. The precipitated deposit is sucked 0E and a} dried in vacuo at about 60 C. 16.0 parts of a brown dyestufi' powder are obtained. This chromium complex of dyes wool from a neutral or weakly acetic bath a slightly bluish red. The dyeing shows a good fastness to rubbing, washing and to light. When employing the 6-bromo- 2-hydroxy-l-naphthaldehyde a dyestufi of similar properties is obtained.

Example 6 10.70 parts of hydroquinone methylene sulfone ether aldehyde and 9.43 parts of 4-nitro-6-chloro-2-aminophenol are heated in 100 parts of formamide for half an hour to about C. 63.2 parts of an aqueous solution of sodium potassium chrome-salicylate corresponding to 1.56 parts of chromium are then run in, and the solution is heated on the boiling water bath for 3 hours. The chromium complex compound of the azomethine dyestutf of the formula OH H? CH=N Cl (S CH: N02

separates in red-brown, fine crystals of metallic lustre which are sucked off at 60 C. and washed with 300 cc. of cold water. After drying 16.5 parts of dyestutf are obtained. The dyestuff dyes wool from a neutral and weakly acetic bath very clear reddish orange shades. The dyeing is fast to rubbing and washing; the levelling power is good.

The hydroquinone methylene sulfone aldehyde CHO is obtained according to the Reimer-Tiemann synthesis by the action of chloroform upon hydroquinone methylene sulfone ether in caustic soda alkaline solution. The aldehyde thus obtained is soluble in alkalies, insoluble in water. Melting-point 240 C.

Example 7 By replacing the quantity of the 4-nitro-6-chloro-2- aminophenol mentioned in Example 6 by 9.95 parts of 4,6-dinitro-2-aminophenol and further carrying out the process as described therein, the brown chromium complex of the azomethine dyestufi of the formula OH HO OH=N N02 is obtained in the form of fine crystals which dyes wool from a neutral and weakly acetic bath clear, full yellowish red shades. Example 8 By replacing the quantity of the 4-nitro-6-chloro-2 aminophenol mentioned in Example 6 by 9.35 parts of 2-aminophenol-4-methylsulfone and carrying out the process as described therein, 12.3 parts of an orange red crystal powder are obtained which dyes wool from a weakly acetic bath very pure clear orange shades. The new dyestufi is the chrome complex of the compound of the formula OH HO Example 9 are obtained which dyes wool from a weakly acetic bath clear bordeaux shades.

Example 10 14.20 parts of naphthohydroquiuone methylene sulfone ether aldehyde and 11.67 parts of Z-amino-l-hydroxybenzene-4-methylsulfone chlorohydrate are heated in 240 parts of formamide and 45 parts of water for half an hour to about 95 C. 63.2 parts of an aqueous solution of sodium-potassium chrome-salicylate corresponding to 1.56 parts of chromium are then run in and the reaction mixture is heated on the boiling Water bath for 3 hours. After cooling the separated chromium complex of the dyestufl of the formula OH H(]) CH=N SO; (Li... 0.

is sucked oh and washed with 500 parts of cold water. After dyeing 14 parts of a red-brown dyestufi powder are obtained. The dyestufi dyes Wool from a weakly acetic bath clear yellowish red shades.

The naphthohydroquinone methylene sulfone ether aldehyde OCH2 CHO

is obtained according to the Reimer-Tiemann synthesis by the action of chloroform upon naphthohydroquinone methylene sulfone ether in caustic soda alkaline solution. The aldehyde is soluble in alkalies, insoluble in water. Melting-point 251 C.

Example 11 By replacing the quantity of 4-nitro-6-chloro-2-aminophenol mentioned in Example 6 by 8.4 parts of 5-nitro-3- amino-4-cresol OgN- NH:

and carrying out the process as described in that ex ample, the chrome complex of the azomethine dyestutf of the formula OH HO OH=N- NO:

l.-.. O... Y

is obtained which dyes Wool from neutral and weakly acetic bath in brownish orange shades. The dyestufi is distinguished by a good levelling power and a very good fastness to light.

Example 12 By replacing the quantity of 4-nitro-6-chloro-2-arninophenol mentioned in Example 6 by 8.4 parts of 5-nitro-3- amino-Z-cresol and carrying out the process as described in that example, the chrome complex of the azornethine dyestutf of the formula OH H? CH=N- CH:

S0 (i)-CH2 l lo:

is obtained which dyes wool from neutral and weakly acetic bath red shades. The fastness to rubbing as well as to light of the dyeings is good.

We claim:

1. Chrome complex compounds of o,o'-dihydroxyazomethine dyestuffs free from sulfonic and carboxylic acid groups corresponding to the general formula wherein the radicals R stand for aromatic radicals selected from the benzene and the naphthalene series, at least one of the radicals R containing a lower alkyl alkyl-sulfone group, and R stands for a member selected from the group consisting of hydrogen and lower alkyl.

2. Chrome complex compounds of o,o-dihydroxyazomethine dyestufis free from sulfonic and carboxylic acid groups corresponding to the general formula wherein the radicals R stand for aromatic radicals selected from the benzene and naphthalene series, at least one of the radicals R containing the divalent radical -SO2'CH2-O linked to two adjacent carbon atoms of the aromatic nucleus.

4. The chrome complex compound of the o,o'-dihydroxyazomethine dyestuff corresponding to the following formula CH=N N:

S 0: I OH;

5. The chrome complex compound of the o,o-dihydroxyazomethine dyestufi corresponding to the following formula CH=N- CH;

O-CH2 6. The chrome complex compound of the o,o-dihydroxyazomethine dyestuff corresponding to the following formula 7. The chrome complex compound of the o,o-dihydroxyazomethine dyestuff corresponding to the following formula CH=N- C1 8. The chrome complex compound of the o,o-dihydroxyazomethine dyestufi' corresponding to the following formula OH HO l I CH=N N0:

7 CH2 N0:

No references cited. 

1. CHROME COMPLEX COMPOUNDS OF O,O'' -DIHYDROXYAZOMETHINE DYESTUFFS FREE FROM SULFONIC AND CARBOXYLIC ACID GROUPS CORRESPONDING TO THE GENERAL FORMULA 